Cationically cross-linkable/polymerizable organic resin composition comprising an iodonium borate and having an acceptable smell

ABSTRACT

A photo-primer composition B is described that includes a specific iodonium salt combined with a hydrogen donor that is a Guerbet alcohol that can also be used as a solvent. The primer system can be used for solving odor problems, particularly after the polymerization/cross-linking of traditional iodonium salts.

The field of the invention is that of compositions used as cationicphotoinitiators in compositions based on organic monomers, oligomersand/or polymers capable of being cationically polymerized or crosslinkedand comprising reactive functional radicals, so as to obtain apolymerized and/or crosslinked film, coating or bulk material (forexample composite).

More specifically, the subject of the present invention is:

-   -   a composition which is polymerizable or crosslinkable        cationically, under activation which is thermal or actinic or by        an electron beam, comprising a photoinitiator composition        according to the invention,    -   a process for producing a film or a coating on a substrate or an        article using the catatonically polymerizable or crosslinkable        composition according to the invention; and    -   a substrate or object of which at least one surface is coated        with a film or a coating obtained from the cationically        polymerizable or crosslinkable composition according to the        invention.

The principle of a photoinduced polymerization or photopolymerizationreaction consists in exposing a composition comprising monomers,oligomers and/or polymers bearing reactive functionalities (such asacrylic, vinyl, epoxy, etc.) to light radiation so as to produce activespecies (free radicals or cations) in order to initiate apolymerization. The generation of these species does not take place bydirect excitation of the monomer, but by means of one or moreadditive(s) contained in the photosensitive formulation and morecommonly denoted “photoinitiator”.

Photoinitiators are categorized in two major families:

-   -   radical photoinitiators, and    -   cationic photoinitiators.

Radical photoinitiators are, inter alia, aromatic ketones which, afterexposure under ultraviolet (UV) radiation:

-   -   undergo hemolytic scission in the a-position with respect to the        carbonyl function (such as for acyl phosphonate derivatives,        acyl phosphine oxide derivatives, benzoin ether derivatives and        acetophenone derivatives) with formation of two radical        fragments, one of which is a benzoyl radical (type I        photoinitiators), or    -   form free radicals when they are promoted in their excited        states by pulling off hydrogen from a hydrogen-donating molecule        (more commonly denoted “coinitiator”), which results in the        formation of an inactive cetyl radical and of an initiator        radical derived from the corresponding donor (type II        photoinitiators).

As examples of type I photoinitiators, mention may be made of: α-hydroxyketones, benzoin ethers, α-aminoaromatic ketones and acylphosphineoxides. As examples of type II photoinitiators, mention may be made of:isopropylthioxanthone (ITX), benzophenone and camphorquinone (CQ). Asexamples of coinitiators, mention may be made of: phenyltetrazolethiol,tris(trimethylsilyl)silene and aromatic amines such as ethyldimethylaminobenzoate (EDB).

The activity of type I or II photoinitiators in radical polymerizationreactions is strongly inhibited by atmospheric oxygen. Indeed, oxygen isknown to have inhibitory properties by energy transfer with respect tothe singlet and triplet excited states of these photoinitiators and byconversion of free radicals into peroxyl radicals devoid of initiatingactivity.

Among cationic photoinitiators, two categories are often distinguisheddepending on whether they release, after photolysis and in the presenceof a hydrogen-donating molecule:

-   -   a Brönsted acid, such as onium salts (diaryliodonium salts,        aryldiazonium salts, alkoxypyridinium salts, triarylsulfonium        salts and sulfonium salts), or    -   a Lewis acid, such as organometallic salts (essentially        ferrocenium salts).

During the photolysis of onium salts, the protonic acid generated iscapable of initiating the cationic polymerization of monomers which donot polymerize via the radical route, such as vinyl ethers orheterocyclic monomers (epoxides, lactones, cyclic ethers,epoxysilicones). The main characteristic of this type of polymerizationis its insensitivity with respect to oxygen, and also its “living”nature. Indeed, the carbocations do not react with one another, suchthat the polymerization, once initiated, will be able to continue indarkness until complete consumption of the monomer.

For onium salts, it is the cationic part which is responsible for theabsorption of the UV radiation, and as regards the anionic part, itdetermines the strength of the acid formed and, consequently, the rateof initiation of the polymerization. The weaker its nucleophilic nature,the faster the photolysis reaction. The various counterfoils used in thecationic photoinitiators can therefore be categorized according to their(decreasing) reactivity:

∘SbF₈ ⁻>(C₈F₅)B⁻>AsF₈ ⁻>PF₈ ⁻>BF₄ ⁻>ClO₄ ⁻.

According to the applications, it is also possible no combine aphotosensitizer with the photoinitiator. A photosensitizer is a moleculewhich absorbs wavelengths different than those absorbed by thephotoinitiator, thus extending their spectral sensitivity.Photosensitization consists of an energy transfer from thephotosensitizer in the excited state to the photoinitiator. Thephotosensitizer increases the fraction of light absorbed by theinitiator and therefore the photolysis yield. Thus, a greater amount ofreactive species are generated and, consequently, the polymerization ismore rapid. As examples of photosensitizers, mention may be made of:anthraquinone, anthracene, pyrene, phenothiazine, benzophenone,acetophenone, xanthones, carbazole derivatives, fluorenone andacylphosphine oxides.

Among the cationic photoinitiators, mention may be made of the iodoniumor sulfonium salts described in U.S. Pat. No. 4,256,828. The referenceEP-0 562 897 describes polymerization or crosslinking initiatorsassociated with monomers, oligomers or polymers comprising reactiveorganofunctional groups in their structure. In particular, document EP-0562 897 describes a composition of which the photoinitiator is insolution at 50% by weight in methanol and has the following structure:

This composition is intended for the production of coatings on a papersubstrate using epoxidized monomers that are polymerized and crosslinkedby irradiation under UV.

In point of fact, it so happens that photoinitiators of iodonium boratetype, while they are particularly effective, nave the major drawback ofbeing formulated using alcoholic solutions, usually in a methanol orisopropanol solution, which presents safety problems associated with theflashpoints of these solvents. Furthermore, the presence of acharacteristic: odor, perhaps due to decomposition of the photoinitiatorafter use thereof, results in an unpleasant perception by users. Thistherefore creates a need to dispense with them, especially in anindustrial environment where production rates are increasingly high. Thesolutions for treating this problem in an industrial environment involvethe use of expensive equipment (ventilation, fume cupboard, etc.).Depending on the facilities and rates used, these odors may even bedescribed as “olfactory pollutions” from the moment that they areperceived as an (excessive) nuisance by users.

It should be noted that, in the present disclosure, the term “odor” willbe defined according to standard ISO 5492—NF EN 13725, which defines itas an organoleptic attribute perceived by means of the olfactory organin sniffing certain volatile substances.

More recently, in order to respond to this problem of unpleasantperception of odor in compositions for inks or varnishes that isassociated with the use of cat ionic photoinitiators of iodonium salttype, patent, application WO2009083564-(A1) proposes the combination ofan iodonium borate-type photoinitiator with a specific category ofphotosensitizers chosen from diether-anthracenes, diether-naphthalenesand diether-benzenes. However, the major drawback associated with thiscombination is the reactivity of the system, which is too low forindustrial use. Indeed, the time required for gel setting of the mass tobe cross linked is between 6 seconds and 120 seconds.

Thus, the industry of varnishes and coatings on a substrate is alwaysseeking a new cationic photoinitiator or a composition that is of use asa cationic photoinitiator:

-   -   making it possible to achieve polymerization/crosslinking        reactivities and rates that are as high as possible, in        particular so as to be able to maintain industrial coating        rates, for example, when it is a question of coatings (inks,        varnishes),    -   and without however presenting problems linked to the presence        of an unpleasant odor according to user perception, thus        avoiding the setting up of expensive technical solutions in        order to solve this problem of olfactory nuisance.

The perception of odor or mixtures of odors is well known empirically.Nevertheless, theoretical knowledge in this field, although it isconstantly progressing, still comes up against the difficulty ofpredicting, for a chemical compound or a mixture of chemical compounds:

-   -   the actual perception of an odor, or of its “olfactory        threshold” which is the minimum concentration producing an odor        perceptible by a panel of individuals,    -   the determination of the pleasurable nature when an odor is        perceived, and    -   the intensity of the odor due to this chemical compound or of        this mixture of chemical compounds.

In these circumstances, one of the essential objectives of the presentinvention is to provide a composition which is polymerizable or crosslinkable cationically, under activation which is thermal or actinic orby an electron beam, using photoinitiator compositions making itpossible to achieve polymerization/cross linking reactivities and ratesthat are as high as possible, in particular so as to be able to use themin the coating industry, such as in inks or varnishes, and withouthowever presenting the problems linked to the presence of an unpleasantodor according to user perception (in particular afterpolymerization/crosslinking), thus avoiding the setting up of expensivetechnical solutions in order to solve this problem of olfactorynuisance.

Another essential objective of the invention is to provide a process forproducing a film or a coating on a substrate or an article using thecomposition according to the invention.

The final object of the invention is to provide a substrate or an objectof which at least one surface is coated with a film or a coatingobtained from the cationically polymerizable or crosslinkablecomposition according to the invention.

These various objectives are achieved by the invention which relatesfirst of ail, in its first subject, to a novel composition R which ispolymerizable and/or crosslinkable cationically, under activation whichis thermal and/or actinic and/or by an electron beam, comprising:

-   -   1) at least one cationically polymerizable and/or crosslinkable        organic compound D not containing a silicon atom;    -   2) an effective catalytic amount of a cationic photoinitiator        composition P comprising:    -   a) at least one iodonium salt A of formula (I)′ below:

wherein:

-   -   the symbols R¹ and R² are identical or different, and each        represent a linear or branched alkyl radical having from 10 to        30 carbon atoms and preferably from 10 to 20 carbon atoms, and        even more preferentially from 10 to 15 carbon atoms,    -   a and b are integers such that 0≦a≦3, 1≦b≦4 and a+b=4,    -   c and c′ are integers, which may be identical or different,        ranging from 1 to 5 and preferably c and c′ are equal to 1,    -   the symbols X, which may be identical or different, represent a        chlorine or fluorine atom with 0≦a≦3, or an OH function with        0≦a≦2, and    -   the symbols R³, which may be identical or different, represent a        phenyl radical substituted with at least 2 halogen atoms, and        preferably with at least 2 fluorine atoms, or at least one        electron-withdrawing group chosen from the group consisting of:        —CF₃, —OCF₃; —NO₂, —CN, —SO₂—C_(n)F_(2n+), —(CO)—C_(n)F_(2n+1),        —O—C_(n)F_(2n+1) and —C_(n)F_(2n+1), with n being an integer        from 1 to 20, or an aryl radical containing at least two        aromatic nuclei, such as biphenyl, naphthyl, optionally        substituted with at least one halogen atom, in particular a        fluorine atom, or an electron-withdrawing group such as: —CF₃,        —OCF₃, —NO₂, —CN, —SO₂—C_(n)F_(2n+), —(CO)—C_(n)F_(2n+1),        —O—C_(n)F_(2n+1), and —C_(n)F(II) _(2n+1), with n being an        integer from 1 to 20,    -   b) at least one hydrogen donor B chosen from the group        consisting of Guerbet alcohols of formula (II) below:

R⁴—CH(CH₂OH)—R^(s)   (II)

wherein:

-   -   the symbols R⁴ and R⁵ are identical or different, and each        represent an alkyl radical having from 4 to 12 carbon atoms, and    -   with the additional condition that the total number of carbon        atoms of said Guerbet alcohol is from 10 to 20 carbon atoms, and    -   c) optionally at least one thermal stabilizer C,    -   3) optionally an effective amount of at least one        photosensitizer E,    -   4) optionally at least one organic solvent F,    -   5) optionally at least one additive Q, and    -   6) optionally at least one thermal stabilizer C.

Preferably, the composition R which is polymerizable and/orcrosslinkable cationically, under activation which is thermal and/oractinic and/or by an electron beam comprises:

-   -   1) at least one cationically polymerizable and/or crosslinkable        organic compound D not containing a silicon atom;    -   2) an effective catalytic amount of a cationic photoinitiator        composition P comprising:    -   a) at least one iodonium salt A of formula (I) below:

wherein:

-   -   the symbols R¹ and R² are identical or different, and each        represent a linear or branched alkyl radical having from 10 to        30 carbon atoms and preferably from 10 to 20 carbon atoms, and        even more preferentially from 10 to 15 carbon atoms,    -   a and b are integers such that 0≦a≦3, 1≦b≦4 and a+b=4,    -   the symbols X, which may be identical or different, represent a        chlorine or fluorine atom with 0≦a≦3, or an OH function with        0≦a≦2, and    -   the symbols R³, which may be identical or different, represent a        phenyl radical substituted with at least 2 halogen atoms, and        preferably with at least 2 fluorine atoms, or at least one        electron-withdrawing group chosen from the group consisting of:        —CF₃, —OCF₃, —NO₂, —CN, —SO₂—C_(n)F_(2n+), —(CO)—C_(n)F_(2n+1),        —O—C_(n)F_(2n+1), and —C_(n)F_(2n+1), with n being an integer        from 1 to 20, or an aryl radical containing at least two        aromatic nuclei, such as biphenyl, naphthyl, optionally        substituted with at least one halogen atom, in particular a        fluorine atom, or an electron-withdrawing group such as: —CF₃,        —OCF₃, —NO₂, —CN, —SO₂—C_(n)F_(2n+), —(CO)—C_(n)F_(2n+1),        —O—C_(n)F_(2n+1) and C_(n)F_(2n+1), with n being an integer from        1 to 20,    -   b) at least one hydrogen donor B chosen from the group        consisting of Guerbet alcohols of formula (II) below:

R⁴—CH(CH₂OH)—R⁵   (II)

wherein:

-   -   the symbols R⁴ and R⁵ are identical or different, and each        represent an alkyl radical having from 4 to 12 carbon atoms, and    -   with the additional condition that the total number of carbon        atoms of said Guerbet alcohol is from 10 to 20 carbon atoms, and    -   c) optionally at least one thermal stabilizer C,    -   3) optionally an effective amount of at least one        photosensitizer E,    -   4) optionally at least one organic solvent F,    -   5) optionally at least one additive Q, and    -   6) optionally at least one thermal stabilizer C,

It is to the credit of the inventors to have selected a combinationbetween a specific photoinitiator which is an iodonium borate having,for its cationic part at the level of its aromatic nuclei, alkyl radicalgroups having from 10 to 30 carbon atoms, and a hydrogen donor B chosenfrom a specific category of alcohols which is that of Guerbet alcohols,such that there are no longer any problems linked to the presence of anunpleasant odor perceived by users and thus avoiding the setting up ofexpensive technical solutions in order to solve this problem ofolfactory nuisance.

Another important advantage concerns the better reactivity of this novelphotoinitiator composition compared with the prior art photoinitiators,thus making it possible to increase coating rates for example when it isa question of coatings (varnishes).

Furthermore, the use of the composition P as a cationic photoinitiatorhas the advantage of decreasing the production of volatile organiccompounds (VOCs) when it is used as a cationic photoinitiator.

The composition P also has the advantage of eliminating the inflammablerisk by conferring on the mixture a high flashpoint, contrary to theiodonium borate photoinitiators of the prior art which are formulated inalcohols such as methanol or isopropanol.

In one preferred embodiment, the Guerbet alcohol according to theinvention may also additionally act as a solvent for the iodonium salt Asuch that the composition P is in the form of a mixture of the iodoniumsalt A in solution in the hydrogen donor B according to the invention.Those skilled in the art will, be able to adjust the concentration ofeach of the constituents and the procedure so as to obtain a more orless concentrated iodonium salt solution.

Preferably, the composition P comprises:

-   -   a) 1 to 95 parts by weight, preferably from 20 to 80 parts by        weight relative to the total weight of the composition P, of the        iodonium salt(s) A,    -   b) 5 to 99 parts by weight, preferably from 20 to 80 parts by        weight relative to the total weight of the composition P, of at        least one hydrogen donor B which is preferably a Guerbet        alcohol, and    -   c) 0 to 5 parts by weight relative to the total weight of the        composition P, of at least one thermal stabilizer C.

Guerbet alcohols are well known and are commercially available. Theyhave the advantage of having low melting points whereas, at equivalentcarbon number, their linear homologs are in the solid state.

According to one preferred embodiment, the hydrogen donor B is a Guerbetalcohol which has the formula below:

wherein n is an integer from 5 to 10 (5, 6, 7, 8, 9 or 10) andpreferably from 6 to 10.

According to another preferred embodiment of the invention, the hydrogendonor B is chosen from the group consisting of the following Guerbetalcohols: 2-butyl-1-octanol, 2-pentyl-1-nonanol, 2-hexyldecan-1-ol,2-octyldecan-1-ol and 2-octyldodecan-1-ol, and mixtures thereof.

According to the nomenclature used, mention may be made of the followingGuerbet alcohols, some of which may be commercially available, in theform of 2 or more constituents in a mixture:

-   -   2-butyl-1-octanol, CAS No.: 3913-02-8, also called:        5-(hydroxymethyl)undecane; Guerbet C₁₂; Guerbet dodecanol;        Isofol® 12 or Jarcol® I-12; available from Sasol Germany,    -   2-pentyl-1-nonanol, CAS No.: 5333-48-2,    -   2-hexyldecan-1-ol, GAS No.: 2425-77-6, Guerbet C₁₆; Guerbet        hexadecanol; Guerbitol 16; Isofol® 16; or Jarcol® I-16,    -   2-octyldecan-1-ol, or octyldecanol (CAS: 70693-04-8) available        from Sasol Germany or which can be found as a mixture under the        name Jarcol® I-18T (mixture of C₁₆, C₁₈ and C₂₀ Guerbet        alcohols), and    -   2-octyldodecan-1-ol, CAS No.: 5333-42-6, or 2-octyl-1-dodecanol        Jarcol® I-20 (the products of the Jarcol® range are sold by the        company Jarchem Innovative Ingredients or are available from the        following companies: Cognis (BASF) Japan or Kao Corporation        Japan.

Preferably, the anion of the iodonium salt A is chosen from the groupconsisting of the following anions: [B(C₆F₅)₄]⁻, [B(C₆H₃(CF₃)₂)₄]⁻,[B(C₆H₄OCF₃)₄]⁻, [B(C₆H₄CF₃)₄]⁻, [(C₆F₅)₂BF₂]⁻, (C₆F₅BF₃]⁻ and[B(C₆H₃F₂)₄]⁻ and preferably from the subgroup consisting of thefollowing anions: B(C₆F₅)₄ ⁻ and [B(C₆H₃ (CF₃)₂)₄ ⁻.

Preferably, for the cationic part of the iodonium salt A, the symbols F¹and R² are identical or different, and each represent an alkyl radicalchosen from the group consisting of the following radicals:

with:

-   -   x is an integer ranging from 6 to 16 and preferably from 6 to        11,    -   y is an integer ranging from 5 to 15 and preferably from 5 to        10, and    -   n and m are integers which may be identical or different and the        sum n+m of which is between 5 and 15 (limits included).

According to the preparation mode used, the iodonium salt A may be inthe form of a mixture of salts of similar structures for the anionicpart, but of varied structures for the cationic part ofalkylphenyliodonium, the alkyl chain of which is linear or branched andcomposed of 10 to 30 carbon atoms and preferably of 10 to 20 carbonatoms, even more preferentially of 10 to 15 carbon atoms, even morepreferentially of 10 to 13 carbon atoms and even more preferentially of12 carbon atoms.

According to one preferred embodiment, the iodonium salt A has theformula (IV) below:

wherein:

-   -   the symbols R¹ and R² are identical or different, and each        represent a linear or branched alkyl radical having from 10 to        30 carbon atoms and preferably from 10 to 20 carbon atoms and        even more preferentially from 10 to 15 carbon atoms.

According to one particularly preferred embodiment, the iodonium salts Aare chosen from the following structures:

The iodonium salt A which is the subject of the present invention may beprepared by exchange reaction between a salt of the cationic entity(halide, such as, for example, chloride or iodide) and an alkali metalsalt of the anionic entity (sodium, lithium or potassium). The operatingconditions (respective amounts of the reagents, choice of the solvents,duration, temperature, stirring) are within the scope of those skilledin the art; said conditions must make it possible to recover the desiredonium borate in solid form by filtration of the precipitate formed or inoily form by extraction using an appropriate solvent. The procedures forsynthesizing the abovementioned cationic entity iodides are known perse. On this subject, see in particular EP-0 562 897. The procedures forsynthesizing the alkali metal salts of the borate anionic entity arealso known per se; in particular, for example, in patent EP-0 562 897.

Advantageously, the composition P according to the invention may beprepared by means of the process comprising the following steps:

-   -   a) precursor salts of formulae (VIII) and (IX) below are        prepared:

in which formulae:

-   -   the symbols R¹ and R² are identical or different, and each        represent a linear or branched alkyl radical having from 10 to        30 carbon atoms and preferably from 10 to 20 carbon atoms and        even more preferentially from 10 to 15 carbon atoms,    -   a and b are integers such that 0≦a≦3, 1≦b≦4 and a+b=4,    -   the symbols X, which may be identical or different, represent:        -   a chlorine or fluorine atom with 0≦a≦3, or        -   an OH function with 0≦a≦2, and    -   the symbols R³, which may be identical or different, represent:    -   a phenyl radical substituted with:        -   at least 2 halogen atoms, and preferably with at least 2            fluorine atoms, or        -   at least one electron-withdrawing group chosen from the            group consisting of: —CF₃, —OCF₃, —NO₂, —CN,            —SO₂—C_(n)F_(2n+), —(CO)—C_(n)F_(2n+1), —O—C_(n)F_(2n+1) and            C_(n)F_(2n+1), with n being an integer from 1 to 20, or    -   an aryl radical containing at least two aromatic nuclei, such as        biphenyl, naphthyl, optionally substituted with at least one        halogen atom, in particular a fluorine atom, or an        electron-withdrawing group such as: —CF₃, —OCF₃, —NO₂, —CN,        —SO₂—C_(n)F_(2n+), —(CO)—C_(n)F_(2n+1), —O—C_(n)F_(2n+1), and        C_(n)F_(2n+1), with n being an integer from 1 to 20,    -   the symbol Z⁺ is a cation of an atom or of a group of atoms and        preferably the symbol Z⁺ is Na⁺, Li⁺ or K⁺, and    -   the symbol Y⁻ is an anion of an atom or of a group of atoms and        preferably Y⁻ is the bromide (Br⁻) or iodide (I⁻) anion,    -   b) a mixture No. 1 is prepared, consisting of a precursor salt        of formula (VIII) and water, and a mixture No. 2 is prepared,        consisting of at least one precursor salt of formula (IX) and at        least one Guerbet alcohol according to the invention and as        described above,    -   c) mixture No. 1 or mixture No. 2 is placed in a reactor with        stirring and optionally under reflux, and the temperature of the        reactor is preferably raised and maintained in a range of        between 30 and 80° C. and even more preferentially in a range of        between 50 and 80° C.,    -   d) then either mixture No. 1, when, in step c), mixture No. 2 is        present in the reactor, or mixture No. 2, when, in step c),        mixture No. 1 is present in the reactor, is added with stirring,        and the temperature of the reactor is preferably maintained in a        range of between 30 and 80° C. and even more preferentially in a        range of between 50 and 80° C.,    -   e) when the reaction has ended, the reactor is optionally cooled        and the organic phase is separated from the aqueous phase,    -   f) optionally, the organic phase is washed with water,    -   g) optionally, the organic phase is devolatilized, and    -   h) the organic phase is recovered, which is the composition P to        which at least one thermal stabilizer C is optionally added.

As examples of precursor salts (VIII), mention may be made of thefollowing salts:

triphenylmethylium tetrakis(pentafluorophenyl)borate (CAS No.:136040-19-2), lithium tetrakis (pentafluoro-phenyl)borate (in its formcomplexed with an ethyl ether ligand, CAS No.: 155543-02-5, sodiumtetrakis-(pentafluorophenyl) borate (CAS No.: 149213-65-05 and potassiumtetrakis(pentafluorophenyl)borate (CAS No.: 89171-23-3) which arewell-known compounds that are commercially available. The preferredprecursor salts of formula (VIII) are sodiumtetrakis(pentafluorophenyl)borate (CAS No.: 149213-65-0) and potassiumtetrakis(pentafluorophenyl)borate (CAS No.: 89171-23-3).

The precursor salts of formula (IX) are well-known compounds that can beprepared according to the protocol described in patent applicationEP-2428501-A1. These precursor salts of formula (IX) may be in the formof a mixture of two or three compounds or more.

According to one preferred embodiment, in step b) of the processaccording to the invention, the preparation with stirring of mixture No.2 consisting of at least one precursor salt of formula (IX) and at leastone Guerbet alcohol is carried out in a reactor at a temperature ofbetween 40 and 85° C. and even more preferentially between 50 and 80°C., then, in step c), the temperature is maintained and, in step d),mixture No. 1 is added to mixture No. 2 while maintaining thetemperature of the reactor between 40 and 85° C. and even morepreferentially between 50 and 80° C.

In one preferred embodiment, the Guerbet alcohol according to theinvention may also additionally act as a solvent for the iodonium salt Asuch that the composition P is in the form of a mixture of the iodoniumsalt A in solution in the hydrogen donor B according to the invention.Those skilled in the art will be able to adjust the concentration ofeach of the constituents so as to obtain a more or less concentratedsolution of at least one precursor salt of the formula (IX) and of atleast one Guerbet alcohol.

One or more thermal stabilizer(s) C may be present in the composition Paccording to the invention or in a composition to be polymerized and/orto be crosslinked and in which the composition P is present and is usedas a cationic photoinitiator. Examples of thermal stabilizers C aredescribed in the article by J. F. Rabek, “Photostabilization ofPolymers; Principles and Applications”, Elsevier Applied Science, NY,1990 or in the reference “Plastics Additives Handbook”, 5th edition,edited by K. Zweifel, Hanser Publishers, 2001.

According to one preferred embodiment of the invention, the thermalstabilizer C is chosen from, the group consisting of; an amine, acompound of which the chemical structure comprises a sterically hinderedgroup and a nitroxyl function, a compound of which the chemicalstructure comprises a sterically hindered, group and a phenol function,an organophosphorus compound, and combinations thereof.

As more specific examples, mention may be made of:

-   -   organic phosphites and phosphonites, such as the following        compounds: triphenyl phosphite, diphenylalkyl phosphites,        phenyldialkyl phosphites, tri(nonylphenyl) phosphite, trilauryl        phosphite, trioctadecyl phosphite, distearyl pentaerythritol        diphosphite, tris(2,4-di-tert-butylphenyl) phosphite,        diisodecylpentaerythritol diphosphite, di(2,        4-di-tert-butylphenyl) pentaerythritol diphosphite,        tristearylsorbitol triphosphate and        tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenyldiphosphonite;    -   examples of organic phosphorus compounds are described in patent        U.S. Pat. No. 6,444,733, phosphorus-containing compounds        comprising sulfide, such as, for example, the following        compounds:        -   trismethylthiophosphite,        -   trisethylthiophosphite,        -   trispropylthiophosphite,        -   trispentylthiophosphite,        -   trishexylthiophosphite,        -   trisheptylthiophosphite,        -   trisoctylthiophosphite,        -   trisnonylthiophosphite,        -   trislaurylthiophosphite,        -   trisphenylthiophosphite,        -   trisbenzylthiophosphite,        -   bispropiothiomethylphosphite,        -   bispropiothiononylphosphite,        -   bisnonylthiomethylphosphite,        -   bisnonylthiobutylphosphite,        -   methylethylthiobutylphosphite,        -   methylethylthiopropiophosphite,        -   methylnonylthiobutylphosphite,        -   methylnonylthiolaurylphosphite, and        -   pentylnonylthiolaurylphosphite; or    -   compounds comprising a sterically hindered group and a nitroxyl        function are, for example, described in patents U.S. Pat. No.        6,337,426 or U.S. Pat. No. 5,254,760;    -   amines comprising sterically hindered groups, such as, for        example, the following compounds: bis(2,2, 6,        6-tetramethyl-piperidyl) sebacate,        bis(1,2,2,6,6-pentamethylpiperidyl) sebacate,        n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonic acid bis        (1,2,2,6,6-pentamethylpiperidyl) ester, the product, of        condensation between        1-hydroxyethyl--2,2,6,6-tetramethyl-4-hydroxypiperidine and        succinic acid, the product of condensation between        N,N′-(2,2,6,6-tetramethylpiperidyl)hexa-methylenediamine and        4-tert-octyl-amino-2,6-dichloro-s-triazine,        tris(2,2,6,6-tetramethylpiperidyl) nitrilotriacetate,        tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,        and 1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetra-methylpiperazinone).        Examples of amine stabilizers comprising sterically hindered        groups and the use thereof are found in documents EP-162524,        EP-920483 or EP-263561.

In general, the added amount of stabilizer varies according to itsnature. By way of indication, amounts of between 1 and 3000 ppm arecommon when sterically hindered amines are involved.

According to the invention, the term “effective catalytic amount” or“effective amount” is intended to mean the amount sufficient to initiatepolymerization and/or cross linking. Depending on the concentration ofiodonium salt A in the composition Pf this amount will foe adjusted soas to add an amount of between 0.01 and 20 parts by weight of iodoniumsalt A, most commonly between 0.05 and 8 parts by weight in order topolymerize and/or crosslink 100 parts by weight of the cationicallypolymerizable and/or crosslinkable organosilicon compound D.

In one preferred embodiment, the compound D is organic in nature andbears organofunctional groups belonging to at least one of the followingspecies:

-   -   α1.1 cycloaliphatic epoxides,    -   α1.2 non-cycloaliphatic epoxides,    -   α2 linear or cyclic alkenyl ethers,    -   α3 polyols, and    -   α4 oxetanes.

As examples of compounds D mention may be made of:

α_(1.1) cycloaliphatic epoxides, taken by themselves or as a mixturewith one another:

-   -   epoxides of the type        3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate:

-   -   bis(3,4-epoxycyclohexyl)adipate;    -   3,4,2-methylcyclohexylmethyl-3,4-epoxy-2-methylcyclohexanecarboxylate;    -   bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, or    -   those mentioned in U.S. Pat. No. 3,117,099,

α_(1.2) non-cycloaliphatic epoxides, taken by themselves or as a mixturewith one another:

-   -   epoxides of the type of those resulting from the condensation of        bisphenol a and of epichiorohydrin, alkoxylated bisphenol A        diglycidyl or triglycidyl ether, or those described in U.S. Pat.        No. 3,018,262,    -   alpha-olefin epoxides, Novolac epoxide, epoxidized soybean and        linseed oil, epoxidized polybutadiene, and more generally a        saturated or unsaturated, epoxidized and monohydroxylated diene        polymer, described in patent application WO-A-96/11215,

α₂ linear or cyclic alkenyl ethers, taken by themselves or as a mixturewith one another:

-   -   vinyl ethers, in particular triethylene glycol divinyl ether,        cyclic vinyl ethers or acrolein tetramers and/or dimers,    -   propenyl ethers,    -   and butenyl ethers, which are more especially preferred,

α₃ polyols: taken by themselves or as a mixture with one another, andpreferably the compound having the formula below, I being greater than 1and less than 100:

where R¹⁶ is a linear or branched. C₁-C₃₀ alklyl radical, and

α₄ bis-oxetanes: such as those described in U.S. Pat. No. 5,721,020.

It is also possible to envision compounds D containing an epoxy(oxirane) group and an oxetane group. Such compounds are described inpatent application DE-196 47 848 A1. As specific example, mention may bemade of: 3-((oxiranylmethoxy)methyl)oxetane or3-alkyl((oxiranylmethoxy)methyl)oxetane wherein the alkyl group containsfrom 1 to 8 carbon atoms.

There are numerous commercial products in particular in the category ofepoxy resins, such as: octadecylene oxide, epichiorohydrin, styreneoxide, vinylcyclohexene oxide, glycidol, glycidyl methacrylate,bisphenol A diglycidyl ether (for example those available under thetrade name Epon 828, Epon 825, Epon 1004 or Epon 1010 from the companyShell Chemical Co., DER-331, DER-332 and DER-334 from the company DowChemical Co.), vinylcyclohexene dioxide (for example ERL-4206 from thecompany Union Carbide Corp.),3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexenecarboxylate (such asERL-4221, Cyracure UVR 6110 or UVR 6105 from the company Union CarbideCorp.),3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexenecarboxylate(such, as ERL-4201 from the company Union Carbide Corp.),bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate (such as ERL-4289 fromthe company Union Carbide Corp.), bis(2,3-epoxycyclopentyl) ether (suchas ERL-0400 from the company Union Carbide Corp.), an aliphatic epoxyderived from polypropylene glycol (such as ERL-4050 and ERL-4052 fromthe company Union Carbide Corp.), an epoxidized polybutadiene (such asOxiron 2001 from the company PMC Corp.), flame-retardant epoxy resins(such as DER-580, an epoxy resin of brominated bisphenol type from thecompany Dow Chemical Co.), phenol-formaldehyde novolac-derived1,4-butanediol diglycidyl ether (such as DEN-431 and DEN-438 from thecompany Dow Chemical Co.), bis(3,4-epoxycyclohexyl) adipate (such asERL-4299 or UVR-6128, from the company Union Carbide Corp.),2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane(such as ERL-4234 from the company Union Carbide Corp.),vinylcyclohexene monoxide 1,2-epoxyhexadecane (such as UVR-6216 from thecompany Union Carbide Corp.) an alkyl glycidyl ether, such as a C₈-C₁₀alkyl glycidyl ether (such as Heloxy Modifier 7 from the company ShellChemical Co.), a C₁₂-C₁₄ alkyl glycidyl ether (such as Heloxy Modifier 8from the company Shell Chemical Co.), a butyl glycidyl ether (such asHeloxy Modifier 61 from the company Shell Chemical Co.), a cresylglycidyl ether (such as Heloxy Modifier 62 from the company ShellChemical Co.), p-tert-butylphenyl glycidyl ether (such as HeloxyModifier 65 from the company Shell Chemical Co.), a neopentyl glycoldiglycidyl ether (such as Heloxy Modifier 68 from the company ShellChemical Co.), a cyclohexanedimethanol diglycidyl ether (such as HeloxyModifier 107 from the company Shell Chemical Co.), trimethyloiethanetriglycidyl ether (such as Heloxy Modifier 44 from the company ShellChemical Co.), trimethylolpropane triglycidyl ether (such as HeloxyModifier 48 from the company Shell Chemical Co.), a polyglycidyl etherof an aliphatic polyol (such as Heloxy Modifier 84 from the companyShell Chemical Co.), a polyglycol diepoxide (such as Heloxy Modifier 32from the company Shell Chemical Co.), bisphenol F epoxides (such asEPN-1138 or GY-281 from the company Ciba-Geigy Corp.) and9,9-bis[4-(2,3-epoxypropoxy)phenyl]fluorenone (such as Epon 1079 fromthe company Shell Chemical Co.).

The monomer, oligomer or polymer H having organofunctional groups ofacrylate kind has, for example, epoxidized acrylate, polyester glycerolacrylate, multifunctional acrylate, urethane acrylate, polyetheracrylate, unsaturated polyester, polyester acrylate or acrylic acrylatefunctions.

These acrylic species, optionally as a mixture, are preferably chosenfrom the following species: trimethylolpropane triacrylate, tripropyleneglycol diacrylate, glycidylpropyl triacrylate, pentaerythritoltriacrylate, trimethylolpropane ethoxylate triacrylate, bisphenol Aethoxylate diacrylate, tripropylene glycol diacrylate, triethyleneglycol diacrylate, tetraethylene glycol diacrylate, polyether acrylates,polyester acrylates (for example the product Ebecryl 810 from thecompany Cytec), and epoxy acrylates (for example the product Ebecryl®600 from the company Cytec).

It is recalled that, in the present report, the expression ‘“acrylic”’encompasses compounds comprising the function of CH₂═CH—(CO)—O— type orof CH₂═C(CH₃)—(CO)—O— type.

The photosensitizer E is chosen from molecules which absorb wavelengthsdifferent than those absorbed by the photoinitiator in order to thusmake it possible to extend their spectral sensitivity. Its mode ofaction is more commonly known as “photosensitization” which consists ofan energy transfer from the excited photosensitizer to thephotoinitiator. Thus, the photosensitizer increases the fraction oflight absorbed by the initiator and therefore the photolysis yield.Thus, a greater amount of reactive species is generated and,consequently, the polymerization is more rapid. There is a large numberof photosensitizers well known to those skilled in the art. Preferably,the photosensitizer will be chosen according to the following criteria:

-   -   The energy of its excited state is greater than that of the        photoinitiator,    -   its absorption spectrum is in a region where fillers and        pigments do not absorb, and    -   it is chemically inert.

As examples of photosensitizers E, mention may be made of: anthracene,pyrene, phenothiazine, Michler's ketone, xanthones, thioxanthones,benzophenone, acetophenone, carbazole derivatives, fluorenone,anthraquinone, camphorquinone or acylphosphine oxides.

In particular, the photosensitizer E can also be chosen:

-   -   from the diether anthracenes having the following formulae:

-   -   from the diether napthalenes having the following formulae:    -   or from the diether benzenes having the following formulae:

These photosensitizers are described in particular in documentWO-A-2006/073021. Mention may also be made of aromatic hydrocarbon-basedphotosensitizers containing one or more substituted or unsubstitutedaromatic nuclei, having a residual absorption of light between 200 and500 nm, such as those of formulae (IV) to (XI) and (XIII) to (XXII)described from page 8 to page 15 of document WO-A-00/19966 or else atleast one of the benzophenones described on page 4, line 33 to page 7,line 12, and page 8, line 9 line 13 of document WO-A-99/05181. By way ofexample, mention may be made of the following compounds:

-   -   4,4′-dimethoxybenzoin; phenanthrenequinone;    -   2- ethylanthraquinone; 2-methylanthraquinone;    -   1,8-dihydroxyanthraquinone; dibenzoyl peroxide;    -   2,2-dimethoxy-2-phenylacetophenone; benzoin;    -   2-hydroxy-2-methylpropiophenone; benzaldehyde;    -   4-(2-hydroxyethoxy)phenyl (2-hydroxy-2-methylpropyl) ketone;        benzoylacetone;

-   -   2-isopropylthioxanthone; 1-chloro-4-propoxythio-xanthone;        4-isopropylthioxanthone; 2,4-diethyl thioxanthone;        camphorquinone; and a mixture thereof.

Other photosensitizers can be used. In particular, use may be made ofthe photosensitizers described in documents U.S. Pat. No. 4,939,069,U.S. Pat. No. 4,278,751 and U.S. Pat. No. 4,147,552.

Mention may also be made of the pbotosensitizers mentioned in patentapplication WO 2005/070989, such as:

-   -   in the thioxanthone family: thioxanthone,        2-isopropylthioxanthone, 2-chlorothioxanthone,        2-dodecylthioxanthone, 2,4-diethylthioxanthone,        2,4-dimethylthioxanthone, 1-methoxycarbonyl-thioxanthone,        2-ethoxycarbonylthioxanthone,        3-(2-methoxyethoxycarbonyl)thioxanthone,        4-butoxycarbonylthioxanthone,        3-butoxycarbonyl-7-methylthioxantnone,        1-chloro-4-propoxythioxanthone, 1-cyano-3-chlorothioxanthone,        1-ethoxycarbonyl-3-chlorotrioxanthone,        1-ethoxycarbonyl-3-ethoxythioxanthone, 1-        ethoxycarbonyl-3-aminothioxanthone,        1-ethoxycarbonyl-3-phenylsulfurylthioxanthone,        3,4-di-[2-(2-methoxyethoxy)ethoxycarbonyl]-thioxanthone,        1-ethoxycarbonyl-3-(1-methyl-1-morpholinoethyl) thioxanthone,        2-methyl-6-dimethoxymethylthioxanthone,        2-methyl-6-(1,1-dimethoxybenzyl) thioxanthone,        2-morpholino-methylthioxanthone,        2-methyl-6-morpholino-methylthioxanthone,        N-allylthioxanthone-3,4-dicarboximide,        N-octylthioxanthone-3,4-dicarboximide,        N-(1,1,3,3-tetramethylbutyl)-thioxanthone-3,4-dicarboximide,        1-phenoxy-thioxanthone, 6-ethoxycarbonyl-2-methoxy-thioxanthone,        6-ethoxycarbonyl-2-methyl-thioxanthone,        1,3-dimethyl-2-hydroxy-9H-tioxanthen-9-one-2-ethylhexyl ether        thioxanthone-2-polyethylene glycol ester,        2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthon-2-yloxy)-N,N,N-trimethyl-1-propanaminiam        chloride;    -   in the benzophenone family: benzophenone, 4-phenylbenzophenone,        4-methoxybenzophenone, 4,4′ -dimethoxybenzophenone,        4,4′-dimethylbenzo-phenone, 4,4′-dichlorobenzophenone,        4,4′-dimethylaminobenzophenone, 4,4′-diethylamino-benzophenone,        4-methylbenzophenone, 2,4,6-trimethylbenzophenone,        4-(4-methylthiophenyl)-benzophenone,        3,3′-dimethyl-4-methoxybenzo-phenone, 2-methylbenzoyl benzoate,        4-(2-hydroxyethylthio)benzophenone, 4-(4-tolylthio-benzoohenone,        4-benzoyl-N,N,N-trimethylbenzene-methanaminium chloride,        2-hydroxy-3-(4-benzoylphenoxy)-N,N,N-trimethyl-1-propanaminium        chloride monohydrate,        4-(13-acryloyl-1,4,7,10,13-pentaoxatridecyl) benzophenone,        4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyl)oxy]ethylbenzenemethanaminium        chloride;    -   in the 3-acylcoumarin family: 3-benzoyl-coumarin,        3-benzoyl-7-methoxycoumarin, 3-benzoyl-5,7-di(propoxy)coumarin,        3-benzoyl-6,8-dichlorocoumarin, 3-benzoyl-6-chloro-coumarin,        3,3′-carbonyl-bis[5,7-di(propoxy)-coumarin],        3,3′-carbonyl-bis[7-methoxy-coumarin), 3,3′-carbonyl-bis        (7-diethylamino-coumarin), 3-isobutyroylcoumarin,        3-benzoyl-5,7-dimethoxycoumarin,        3-benzoyl-5,7-diethoxy-coumarin, 3-benzoyl-5,7-dibutoxycoumarin,        3-benzoyl-5,7-di(methoxyethoxy) coumarin,        3-benzoyl-5,7-di(allyloxy) coumarin,        3-benzoyl-7-dimethylaminocoumarin,        3-benzoyl-7-diethyl-aminocoumarin,        3-isobutyroyl-7-dimethylamino-coumarin,        5,7-dimethoxy-3-(1-naphthoyl)-coumarin,        3,7-dimethoxy-3-(1-naphthoyl)-coumarin,        3-benzoylbenzo[f]coumarin, 7-diethyl-amino-3-thienoylcoumarin,        3-(4-cyanobenzoyl)-5,7-dimethoxycoumarin;    -   in the 3-(aroylmethylene)thiazoline family:        3-methyl-2-benzoylmethylene-5-napthothiazoline,        3-methyl-2-benzoylmethylenebenzothiazoline,        3-ethyl-2-propionylmethylene-p-naphtho-thiazoline;    -   or in the ketone family: acetophenone, 3-ethoxyacetophenone,        4-phenylacetophenone, Benzyl-2-acetylnaphthalene,        2-naphthaldehyde, 9,10-anthraquinone, 9-fluorene,        dibenzo-suberone, xanthone, 2,5-bis(4-diethylaminobenzylidene)        cyclopentanone, α-(para-dimethylaminobenzylidene) ketones, such        as 2-(4-dimethylaminobenzylidene)indan-1-one or        3-(4-dimethylaminophenyl)-1-indan-5-ylpropenone,        2-benzoyl-3-(4-dimethylaminophenyl) 2-propenenitrile,        3-phenylthiophthalimide, N-methyl-3,5-di(ethylthio)phthalimide        and N-methyl-3,5-di(ethylthio)phthalimide.

Other examples of photosensitizers are described in U.S. Pat. No.6,025,406. When it is present in the composition, the photosensitizer isadded in an amount of from 0.05% to 10% by weight relative to the totalweight of the composition to be poiymerized/crosslinked and preferablybetween 0.1% and 2% by weight relative to the total weight of thecomposition to be polymerized/cross linked.

As examples of additive Q, mention may be made of adhesion modulators(linear silicone resins or polymers bearing vinyl, epoxy, vinyl ether,hydroxyl, etc., functions), pigments, inorganic fillers such as, inparticular, synthetic fibers (polymers) or natural fibers which havebeen ground, calcium, carbonate, talc, clay, titanium dioxide,precipitated or fumed silica; soluble dyes; oxidation and corrosioninhibitors; fungicidal, bactericidal, antimicrobial agents; and/or anyother material which does not interfere with the catalytic activity ofthe initiator and which does not absorb in the wavelength range chosenfor the photoactivation.

The cationically polymerizable and/or crosslinkable composition R can beused as it is or in solution in an organic solvent F. It is of use as athin layer in the field of coatings, in paints, and also as a thicklayer for encapsulating electrical and electronic components, coatingsfor textiles, and inks.

When it is a question of inks, the composition R may also comprise waterso as to control the viscosity. In addition, pigments and/or dyes may beincorporated into the composition R in order to produce water-based inkshaving excellent rheology, which are suitable for a broad range ofprinting applications ranging from Inkjet inks to pasty inks with ahigher viscosity. In the ink applications, it is also possible to addadjuvants well known to those skilled in the art, such as surfactants,leveling agents, wetting agents, dispersants, antifoams, etc.

The expression “under activation which is actinic” means that thecomposition is activated by radiation having a wavelength range fromapproximately 190 nm to approximately 400 nm. Actinic radiation of thistype can be obtained from numerous sources, for example mercury arclamps, xenon arc lamps, fluorescent lamps or monochromatic lasersources.

According to one particular embodiment, the crosslinking operation iscarried out by UV radiation having a wavelength of about 200 to 400nanometers. The irradiation time may be short and it is generally lessthan 1 second and is about a few hundredths of a second for smallcoating thicknesses. The crosslinking obtained is excellent even in theabsence of any heating. Of course, heating between 25 and 200° C. is notexcluded from the invention. Of course, the curing time can be adjustedin particular by the number of UV lamps used, by the UV exposure timeand by the distance between the composition arid the UV lamp. Thecompositions R according to the invention without solvent, i.e.undiluted, are applied using devices capable of uniformly depositingsmall amounts of liquids. For this purpose, it is possible to use, forexample, the device known as “Sliding helio” containing, in particular,two superimposed cylinders: the role of the bottommost cylinder, whichis immersed in the coating tank containing the composition, is toimpregnate the uppermost cylinder with a very thin layer. The role ofthe uppermost layer is then to deposit the desired amounts ofcomposition with which it is impregnated on the substrate, for example apaper substrate. Such quantitative charging is obtained by adjusting therespective speed of the two cylinders which rotate in oppositedirections with respect to one another. The amounts of compositionsdeposited on the substrates are variable and most often range between0.1 and 5 g/m² of surface treated. These amounts depend on the nature ofthe substrates and on the desired non-stick properties. They are mostoften between 0.5 and 1.5 g/m² for non-porous substrates.

The cationically polymerizable and/or crosslinkable composition R of theinvention may also be used in thicker layers (>5 micrometers), as atropicalization varnish (“conformal coating”), the role of which is toelectrically insulate the components and the circuits of an assembly andto keep them sheltered from the external environment and from themechanical factors which can compromise the performance level of theassembly. Said composition can then be applied by spraying or byimmersion, or else by brushing; the thicknesses of the coatings thusformed depend on the method of application chosen and most often varyfrom 5 micrometers to a few tenths of a millimeter; a subsequentpolymerization step may, in certain cases, be necessary; the latter canbe accomplished by a heat treatment.

The invention also relates to a process for producing a hard film orcoating, comprising the following steps:

-   -   1. preparing a cationically polymerizable and/or crosslinkable        composition R as defined in any one of claims 1 to 11;    -   2. applying the mixture obtained to a support; and    -   3. hardening the composition by polymerization and/or        crosslinking into a film or coating thermally or actinically.

A subject of the present invention is also a film or coating obtainedfrom the crosslinking of the composition R according to the inventionand as defined above, thermally or actinically. Another subject of theinvention consists of an article, at least one surface of which iscoated with a film, or a coating obtained according to the processaccording to the invention and as defined, above. This will involve, forexample, articles (sheets for example) consisting of a solid material(metal, glass, plastic, paper, etc.), at least one surface of which iscoated with the composition R described above and crosslinked thermallyor actinically.

Another subject of the invention, consists of a printing ink preparedfrom the composition R according to fine invention and as describedabove.

Finally, the last subject of the invention consists of a substrate orobject, at least one of the surfaces of which is coated with a film or acoating according to the invention and as defined above.

The following examples are given by way of illustration. They will makeit possible in particular to understand the invention more clearly, toreveal ail its advantages and to see some of its implementationvariants.

EXAMPLES 1) Synthesis of the Photoinitiator [(C₁₂H₂₅)—Ph—I—Ph(C₁₂H₂₅)]⁺;^(−B[C) ₆₆F₅]₄ and Preparation of a Composition That is of Use as aCationic Photoinitiator According to the Invention

Dodecylbenzene (100 g; 0.45 mol), potassium iodate (43.5 g; 0.203 mol),acetic acid (199.6 g) and acetic anhydride (59.5 g) are charged to a1-liter round-bottom flask equipped with a mechanical stirrer, awater-cooled reflux condenser and a dropping funnel.

The mixture is stirred and cooled in an ice bath at 0° C. The droppingtunnel is charged with a mixture of sulfuric acid (59.8 g) and aceticacid (39.86 g). This mixture is added to the reaction mass over thecourse of 25 minutes. The mixture is then allowed to return to ambienttemperature (20° C.), and is then left to stir at ambient temperaturefor 18 hours. Water (750 ml) is then added and the reaction mass is thenextracted with three fractions of ether (3×350 ml). The ethereal phasesare combined and then evaporated under reduced pressure. The concentrateis taken up with a saturated solution of sodium chloride (540 ml), andthen the mixture is cooled in an ice bath for two hours. The product isrecovered by filtration through sintered glass No. 4. The solid is thenrecrystallized twice from acetone and bisdodecylphenyliodonium chlorideis recovered by filtration, 13.05 g of the previous compound, 14.36 g ofpotassium tetrakis(pentafluorobenzene)borate and 160 g of methanol aretaken and stirring is carried out for half an hour at ambienttemperature in the dark. The mixture is left to stand for 12 hours andfiltration is carried out followed by devolatilization at 60° C. under0.8 bar.

The product A1 obtained is an oil, there being 25.8 g. Thisphotoinitiator is then mixed into a Guerbet alcohol so as to obtain acomposition chat is of use as a cationic photoinitiator according to theinvention.

2) Synthesis of the Photoinitiator [(C_(n)H_(2n+1))—Ph—I—Ph(C_(n)H_(2n+1))]⁺; ^(−B[C) ₆F₅]₄ n=10−13 and Preparation of aComposition That is of Use as a Cationic Photoinitiator According to theInvention

A (C₁₀C₁₃) alkylbenzene fraction (100 g), potassium iodate (43.5 g;0.203 mol), acetic acid (199.6 g) and acetic anhydride (59.5 g) arecharged to a 1-liter round-bottom flask equipped with a mechanicalstirrer, a water-cooled reflux condenser and a dropping funnel. Themixture is stirred and cooled in an ice bath at 0° C. A mixture ofsulfuric acid (59.8 g) and acetic acid (39.86 g) is charged to thedropping funnel. This mixture is added to the reaction mass over thecourse of 25 minutes. The mixture is then allowed to return to ambienttemperature, and then left to stir at ambient temperature for 18 hours.750 ml of water are then added and the reaction mass is then extractedwith three fractions of ether (3×350 ml). The ethereal phases arecombined and then evaporated under reduced pressure. The concentrate istaken up with a 10% sodium tetrakis(pentafluorobenzene)borate solution(1500 ml), and then left to react in the dark with slow stirring for 12hours. The reaction mass is extracted with three fractions of ether(3×350 ml).

The ethereal phases are combined and then evaporated under reducedpressure.

The product A2, which is an oil, is obtained (225.3 g).

The NMR analysis shows a distribution of C₁₀-C₁₃ alkylbenzene with amixture of three products (63%, 20% and 17% by weight) which differ fromone another by virtue of their cationic part. This photoinitiator isthen mixed into a Guerbet alcohol so as to obtain a composition that isof use as a cationic photoinitiator according to the invention.

3) Preparation Process According to the Invention: Synthesis of thePhotoinitiator [(C_(n)H_(2n+1))—Ph—I—Ph (C_(n)H_(2n+1))]⁺; ⁻B[C₆F₅]₄n=10−13 Directly in a Guerbet Alcohol

The manipulations (tests 1, 2 and 3; are carried out in a three-neckedround-bottom flask equipped with a reflux condenser, a dropping funneland a thermometer probe according to the following protocol (therespective amounts of the constituents are mentioned in Tables 1 and 2):

-   -   An amount of bis (C₁₀₋₁₃) alkylphenyliodonium iodide and then        the Guerbet alcohol Isofol® 20 (octyldodecanol) are charged,        followed by mechanical stirring (510 rpm),    -   heating is carried out at 65° C. while awaiting total        solubilization of the bis(C₁₀₋₁₃) alkylphenyliodonium iodide,    -   the aqueous solution of sodium tetrakis(pentafluorophenyl)        borate is run in,    -   the mixture is left to stir for 4 h at 65° C.,    -   the mixture is transferred into a separating funnel and, after a        return to ambient temperature (over a period of 24 h), the        phases are separated,    -   the organic phase is washed 3 times with 100 g of deionized        water,    -   and the organic phase is devoiatilized: for 4 h, at 70° C.,        under reduced pressure at 5 mbar so as to obtain the composition        that is of use as a cationic photoinitiator according to the        invention.

TABLE 1 Preparation of compositions that are of use as cationicphotoinitiator (20% by mass of iodonium salt in the Guerbet alcoholIsofol

 20 - octyldodecanol) Test 1 Test 2 Mass Amount Mass Amount (g) (mol)(g) (mol) Guerbet alcohol Isofol

50.09 0.168 50.02 0.168 20 (octyldodecanol) bis(C₁₀₋₁₃)alkylphenyl- 7.18 9.84 × 10⁻³ 7.11  9.74 × 10⁻³ iodonium iodide Aqueous solution at 74.511.04 × 10⁻³ — — 10.4% by mass of sodium tetrakis(pentafluoro-phenyl)borate Aqueous solution at — — 155.09 10.16 × 10⁻³ 4.6% by massof sodium tetrakis(pentafluoro- phenyl)borate

indicates data missing or illegible when filed

TABLE 2 Preparation of a composition that is of use as a cationicphotoinitiator (50% by mass of iodonium salt in the Guerbet alcoholIsofol

 20 - octyldodecanol) Test 3 Mass (g) Amount (mol) Guerbet alcoholIsofol

 20 15.02 0.050 (octyldodecanol) bis(C₁₀₋₁₃)alkylphenyliodonium 7.11 9.74 × 10⁻³ iodide Aqueous solution at 10.4% by 74.5 11.04 × 10⁻³ massof sodium tetrakis(penta- fluorophenyl)borate

indicates data missing or illegible when filed

4) Mass Reactivity Under Ultraviolet Radiation

For these examples, the cationically polymerizable and/or crosslinkableorganic compound D not containing a silicon atom is the compound3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate [RNCAS=2385-87-0]. More particularly, a commercial sample from DowChemical, UVR-6105, is used.

TABLE 3 Structures of the various products used in the testsConstituents Chemical structures A2 Iodonium salt (invention)

A- comp Iodonium salt (comparative)

F Isopropanol CH₃—CH(OH)—CH₃ (solvent/hydrogen donor comparative) I1Butyloctanol (Guerbet C₁₂)

I2 Octyldodecanol (Guerbet C₂₀) (solvent/hydrogen donor invention)

Mixtures of iodonium salt/solvent/hydrogen donor+organic compound D areprepared, 1.4 g of each mixture is then placed in a tank ofpolymethylmethacrylate (PMMA). A vibrating needle (frequency 100 Hz) isimmersed in this tank to a depth of 2 mm from the bottom. Thepolymerization reaction is initiated when the bottom of the tank issubjected to UV radiation by means of an optical fiber. With thepolymerization advancing, the viscosity of the medium increased until agel is obtained. This increase in viscosity creates a resistance to thevibration of the needle. This leads to a difference in potential whichmakes it possible to determine the gel time. The mixtures produced usean equimolar amount of iodonium salt A2 (invention) or of anotheriodonium salt A-comp (comparative), i.e. 0.088 mmol for 20 g of thesystem to be UV-polymerized (constituent D) and thus allow a directcomparison of the efficiency of the compositions tested asphotoinitiator.

The snow that the use of a photoinitiator composition according to theinvention makes it possible to very substantially improve the reactivityof the system to be polymerized.

5) Stability of the Photoinitiator Compositions Using the VariousSolvents

Table 4 below summarizes the tests for stability with respect to agingof the photoinitiator compositions obtained by mixing from 40% to 50% byweight by mass of photoinitiator A2 in various Guerbet alcohols (I1 andI2). The aging is accelerated by applying a temperature of 60° C. for 15days.

TABLE 5 Stability with respect to aging of the photoinitiatorcompositions according to the invention Test Solution after Solutionafter No. Solvent 1 day 15 days at 60° C. 12 I1 Clear, liquid Clear,liquid 13 I2 Clear, liquid Clear, liquid

Tests 12 and 13 show that the photoinitiator compositions according tothe invention remain homogeneous and stable with respect to aging,

6) Stabilization of the Photoinitiator Composition

A variable amount of stabilizer (Tinavin® 292 from the company CIBA,which is a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacateand 1-(methyl)-8-(1,2,2,6,6-piperidinyl) sebacate) is added to aphotoinitiator composition containing 70% by mass of iodonium salt A2and 30% by mass of a C₂₀ Guerbet alcohol (I2). These variouscompositions are stored at 20, 40 and 60° C., pH measurements (0.175 gof the photoinitiator composition in 15 g of isopropanol) are carriedout. The pH-meter used (Schott, CG825) is equipped with a glasselectrode (Schott Instruments, N52A) which is calibrated before eachmeasurement series with buffer solutions of pH=4 and pH=7. The pH valuesare noted after the solutions have been left to stand for 5 minutesfollowing stirring for 3 minutes with a magnetic bar.

TABLE 5 Stability with respect to aging of the photoinitiatorcompositions according to the invention pH pH after pH after Storageafter 1 4 weeks 8 weeks Test Stabilizer temperature Initial week of ofof No. (ppm) (° C.) pH storage storage storage 14 0 20 5.67 5.88 6.285.60 15 0 40 5.67 5.91 6.19 6.08 16 0 60 5.67 5.81 3.21 2.83 17 1007 206.35 6.08 6.24 5.87 18 1007 40 6.35 5.90 5.97 5.64 19 1007 60 6.35 5.615.36 3.58 20 4941 20 6.89 6.52 6.44 6.14 21 4941 40 6.89 6.19 5.96 5.8022 4941 60 6.89 5.75 5.25 4.53

Tests No. 19 and 22 show that the addition of a stabilizer to aphotoinitiator composition according to the invention makes it possibleto stabilize the pH during storage over a long period of time. A pHvalue that is too low (below 4) makes the solution unusable in cationicsystems which are reactive under UV.

7) Impact on the Odor of the Final Product and During Coating

Numerous coatings presented above were evaluated according to thefollowing method: 0.5 m² of substrate is recovered at the machineoutlet, immediately after coating and insulation using UV lamps. Thissample is placed in a hermetically closed, clean 1-liter jam jar. After24, a panel of four individuals evaluates, blind, the intensity of theodor perceived in this jam jar.

The coatings were carried out as presented above. The grades 0 to 5given by the experimenters are added. Thus, the lowest value correspondsto the least pronounced odor and vice versa for the highest grade. Thetests according to the invention (Inv.) exhibit a weaker odor than thecomparative tests which use the photoinitiator A-Comp in isopropanol,which is an iodonium salt widely used in the cationic coating industry.

1. A composition R which is polymerizable and/or crosslinkablecationically, under activation which is thermal and/or actinic and/or byan electron beam, the composition comprising: 1) at least onecatatonically polymerizable and/or crosslinkable organic compound D thatdoes not contain a silicon atom; 2) an effective catalytic amount of acationic photoinitiator composition P comprising: a) at least oneiodonium salt A of formula (I)′ below:

wherein: the symbols R¹ and R² are identical or different, and eachrepresent a linear or branched alkyl radical having from 10 to 30 carbonatoms, a and b are integers such that 0≦a≦3, 1≦b≦4 and a+b=4, c and c′are integers, which are identical or different, ranging from 1 to 5, thesymbols X, which are identical or different, represent a chlorine orfluorine atom with 0≦a≦3, or an OH function with 0≦a≦2, and the symbolsR³, which are identical or different, represent a phenyl radicalsubstituted with at least 2 halogen atoms, or at least oneelectron-withdrawing group selected from the group consisting of: —CF₃,—OCF₃, —NO₂, —CN, —SO₂—C_(n)F_(2n+), —(CO)—C_(n)F_(2n+1),—O—C_(n)F_(2n+1) and —C_(n)F_(2n+1), with n being an integer from 1 to20, or an aryl radical containing at least two aromatic nuclei,optionally substituted with at least one halogen atom or anelectron-withdrawing group selected form the group consisting of: —CF₃,—OCF₃, —NO₂, —CN, —SO₂—C_(n)F_(2n+), —(CO)—C_(n)F_(2n+1),—O—C_(n)F_(2n+1) and —C_(n)F_(2n+1), with n being an integer from 1 to20, b) at least one hydrogen donor B selected from the group consistingof Guerbet alcohols of formula (II) below:R⁴—CH(CH₂OH)—R⁵   (II) wherein: the symbols R⁴ and R⁵ are identical ordifferent, and each represent an alkyl radical having from 4 to 12carbon atoms, and with the additional condition that the total number ofcarbon atoms of said Guerbet alcohol is from 10 to 20 carbon atoms, andc) optionally at least one thermal stabilizer C, 3) optionally aneffective amount of at least one photosensitizer E, 4) optionally atleast one organic solvent F, 5) optionally at least one additive q, and6) optionally at least one thermal stabilizer C.
 2. The composition R asclaimed in claim 1, comprising: 1) at least one cationicallypolymerizable and/or crosslinkable organic compound D that does notcontain a silicon atom; 2) an effective catalytic amount of a cationicphotoinitiator composition P comprising: a) at least one iodonium salt Aof formula (I) below:

wherein: the symbols R¹ and R² are identical or different, and eachrepresent a linear or branched alkyl radical having from 10 to 30 carbonatoms a and b are integers such that 0≦a≦3, 1≦b≦4 and a+b=4, the symbolsX, which are identical or different, represent a chlorine or fluorineatom with 0≦a≦3, or an OH function with 0≦a≦2, and the symbols R³, whichare identical or different, represent a phenyl radical substituted withat least 2 halogen atoms or at least one electron-withdrawing groupselected from the group consisting of: —CF₃, —OCF₃, —NO₂, —CN,—SO₂—C_(n)F_(2n+), —(CO)—C_(n)F_(2n+1), —O—C_(n)F_(2n+1) and—C_(n)F_(2n+1), with n being an integer from 1 to 20, or an aryl radicalcontaining at least two aromatic nuclei, optionally substituted with atleast one halogen atom or an electron-withdrawing group selected fromthe group consisting of: —CF₃, —OCF₃, —NO₂, —CN, —SO₂—C_(n) _(F) _(2n+),—(CO)—C_(n)F_(2n+1), —O—C_(nF) _(2n+1) and C_(n)F_(2n+1), with n beingan integer from 1 to 20, b) at least one hydrogen donor B selected fromthe group consisting of Guerbet alcohols of formula (II) below:R⁴—CH(CH₂OH)—R⁵   (II) wherein: the symbols R⁴ and R⁵ are identical ordifferent, and each represent an alkyl radical having from 4 to 12carbon atoms, and with the additional condition that the total number ofcarbon atoms of said Guerbet alcohol is from 10 to 20 carbon atoms, andc) optionally at least one thermal stabilizer C, 3) optionally aneffective amount of at least one photosensitizer E, 4) optionally atleast one organic solvent F, 5) optionally at least one additive q, and6) optionally at least one thermal stabilizer C.
 3. The composition R asclaimed in claim 1, wherein the anion of the iodonium salt A is selectedfrom the group consisting of the following anions: [B(C₆F₅)₄]⁻,[B(C₆H₃(CF₃)₂)₄]⁻, [B(C₆H₄OCF₃)₄]⁻, [B(C₆H₄CF₃)₄]⁻, [(C₆F₅)₂BF₂]⁻,(C₆F₅BF₃]⁻ and [B(C₆H₃F₂)₄]⁻ ₄ ⁻.
 4. The composition R as claimed inclaim 1, wherein the hydrogen donor B is a Guerbet alcohol which has theformula below:

wherein the symbol n is an integer from 5 to
 10. 5. The composition R asclaimed in claim 1, wherein the hydrogen donor B is selected from thegroup consisting of the following Guerbet alcohols: 2-butyl-1-octanol,2-pentyl-1-nonanol, 2-hexyldecan-1-ol, 2-octyldecan-1-ol and2-octyldodecan-1-ol, and mixtures thereof.
 6. The composition R asclaimed in claim 1, wherein the catonic photoinitiator composition Pcomprises: a) 1 to 95 parts by weight relative to the total weight ofthe composition P, of the iodonium salt(s) A, b) 5 to 99 parts by weightrelative to the total weight of the composition P, of at least onehydrogen donor B, and c) 0 to 5 parts by weight relative to the totalweight of the composition P, of at least one thermal stabilizer C. 7.The composition R as claimed in claim 1, wherein the thermal stabilizerC is selected from the group consisting of: an amine, a compound ofwhich the chemical structure comprises a sterically hindered group and anitroxyl function, a compound of which the chemical structure comprisesa sterically hindered group and a phenol function, an organophosphoruscompound, and combinations thereof.
 8. The composition R as claimed inclaim 1, wherein the iodonium salt A has the formula (IV) below:

wherein: the symbols R¹ and R² are identical or different, and eachrepresent a linear or branched alkyl radical having from 10 to 30 carbonatoms.
 9. The composition R as claimed in claim 1, wherein the symbolsR¹ and R² are identical or different, and each represent an alkylradical selected from the group consisting of the following radicals:

wherein: x is an integer ranging from 6 to 16, y is an integer rangingfrom 5 to 15, and n and m are integers which are identical or differentand the sum n+m of which is between 5 and 15 (limits included).
 10. Thecomposition R as claimed in claim 1, wherein the catatonicallypolymerizable and/or crosslinkable organic compound D is a monomer,oligomer and/or polymer which is organic in nature and bearsorganofunctional groups belonging to at least one of the followingspecies: α1.1 cycloaliphatic epoxides, taken by themselves or as amixture with one another, α1.2 non-cycloaliphatic epoxides, taken bythemselves or as a mixture with one another, α2 linear or cyclic alkenylethers, taken by themselves or as a mixture with one another, α3polyols: taken by themselves or as a mixture with one another, or α4bis-oxetanes.
 11. The composition R as claimed in claim 1, wherein thecationically polymerizable and/or crosslinkable organic compound D isthe compound 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylatehaving the following structure:


12. A process for producing a hard film or coating, the processcomprising the following steps: a) preparing a cationicallypolymerizable and/or crosslinkable composition R as defined in claim 1;b). applying the mixture obtained to a support; and c). hardening thecomposition by polymerization and/or crosslinking into a film or coatingthermally or actinically.
 13. A film or coating obtained from thecrosslinking of the composition R as defined in claim 1, thermally oractinically.
 14. An article, at least one surface of which is coatedwith a film or a coating obtained according to the process defined inclaim
 1. 15. A printing ink prepared from the composition R as describedin claim
 1. 16. The composition R as claimed in claim 1, wherein R¹ andR² have from 10 to 20 carbon atoms.
 17. The composition R as claimed inclaim 1, wherein R¹ and R² have from 10 to 15 carbon atoms.
 18. Thecomposition R as claimed in claim 1, wherein c and c′ are equal to 1.19. The composition R as claimed in claim 1, wherein when R³ is a phenylradical substituted with at least 2 halogens, the at least 2 halogensare at least 2 fluorine atoms.
 20. The composition R as claimed in claim1, wherein when R³ is an aryl radical containing at least 2 aromaticnuclei, the at least 2 aromatic nuclei are selected from the groupconsisting of biphenyl and naphthyl.
 21. The composition R as claimed inclaim 1, wherein when R³ is an aryl radical substituted with at least 1halogen, the at least 1 halogen is a fluorine atom.
 22. The compositionR as claimed in claim 2, wherein R¹ and R² have from 10 to 20 carbonatoms.
 23. The composition R as claimed in claim 2, wherein R¹ and R²have from 10 to 15 carbon atoms.
 24. The composition R as claimed inclaim 2, wherein when R³ is a phenyl radical substituted with at least 2halogens, the at least 2 halogens are at least 2 fluorine atoms.
 25. Thecomposition R as claimed in claim 2, wherein when R³ is an aryl radicalcontaining at least 2 aromatic nuclei, the at least 2 aromatic nucleiare selected from the group consisting of biphenyl and naphthyl.
 26. Thecomposition R as claimed in claim 2, wherein when R³ is an aryl radicalsubstituted with at least 1 halogen, the at least one halogen is afluorine atom.
 27. The composition R as claimed in claim 3, wherein theanion of the iodonium salt A is [B(C₆F₅)₄]⁻ or [B(C₆H₃(CF₃)₂)₄]⁻. 28.The composition R as claimed in claim 6, wherein composition P comprises20 to 80 parts by weight of the iodonium salt(s) A.
 29. The compositionR as claimed in claim 6, wherein composition P comprises 20 to 80 partsby weight of the at least one halogen donor B.
 30. The composition R asclaimed in claim 8, wherein R¹ and R² have from 10 to 20 carbon atoms.31. The composition R as claimed in claim 8, wherein R¹ and R² have from10 to 15 carbon atoms.
 32. The composition R as claimed in claim 9,wherein x is an integer ranging from 6 to
 11. 33. The composition R asclaimed in claim 9, wherein y is an integer ranging from 5 to 11.